Composition of matter



Patented Nov. 21, 1944 4UNITEDAS IE "QFFICEm a 1 a aosrgg j 9 aCOMPOSITION QFMATTERI I Gwynne Allen,,,Long Bath; ,Calif assignor toPetroliteUorporation, Ltd; 1st: Louis,v Mo., a I corporation ofDelaware] 1 No Drawing. Application May 27,1942, l i

The object of this invention is to provide" a new material orcomposition of matter which is particularly adapted for use as ademulsifier inY-the resolution of crude oil emulsions and asabreakinducer in the doctor treatment of gasoline, but

, August 10, 1943; Serial No. 444,762, which subsequently matured as U.S. Patent No. 2,329,025, dated September 7, 1943;app1ication Serial No.444,764, which subsequently matured as U. S. PatentNo. 2.,326,602, datedAugust 10, 1943;410- pending application Serial No. 444,765jand ap-Serial No. 444,763

wa (01. ze o-402.5) r g C N Molecular; weight determinations showjthepresence of polymers',;. including ,diads and triads (dimers, trimersl,etc. 1 Destruction ofthe po1y-.

merictbody for example bysaponificatmn with Lalkali,results:, in :a:reduction ,of th molecular weight, "loss of ;the elastic propertieswand,ap-

parently, a return to a simpler addition product.

Inpreparingmy material, I make-no claim to the use of thesimplejunpolymerizedaddition [product'x ofy sulfurandran; unsaturatedhigh molal monocarboxylic detergent-formingacid having, at "least 8, andnot more than32, carbon atoms, typifiedby sulfurized roleicacidr. Imakeno claim plication Serial No. 444,766, which subsequently more than32, carbon for example with oleic acid, the sulfur adds at the doublebond in the oleicacid chain or radical.

Where the oleic acid is employed in combination with a polyhydricalcohol, such as glycerol, as for tojthe use of the freedetergent-forming carboxylic acidyand,sulfuralone' in preparing myreagent; but1I employ the acid only in combinautionvwithafipolyhydricalcohol compound containing two or morealcoholiformhydroxyl groups, in the form of an ester of such acid andsuch 20,. i

polyhydric alcohol.

" The compound containing the ,two- Ormore alcoholiiorm: hydroxyl groupsmaybe a simple poly- .hydric' alcohol; such for exampl 'asglycerol orethylene glycol; or it may be a Condensed poly-- hydric alcohol likepolyglycerol, di-ethylene glyl 001,. di-glycerol, on tri-glycerol; :yIn'addition to wtheiabove :polyhydric alcohols, I may also, use

mannitan, sorbitan, pentaerythritol, and' dipentaerythritol. Imay;useether alcohols so long example in triolein which is thetri-glyceride of oleic acid, the reaction apparently does not stop withthe formation of a simple addition product. Instead, as discussed in theliterature, e. g., Knight and Stamberger, J. ChemJS oc. London, 1928,pp. 2791-8, triolein takes up additional'sulas theyhavetwo or morehydroxyl' g'roupsin the "moleculeji e. (polyhydric alcohols in which acarbon atom chain' is interrupted at least once by to'xygen, asexemplified by di-ethylene glycolprevi- "ously mentioned) .M'Ihey areallcharacterized by i fcontaining twoflor'ln'ore alcoholiformhydroxylgroups andiby having the power to. form esters Mwith' an unsaturated 1high molal monocarboxylic detergent-forming acid having atleastS, andnot *wmore than 32, carbon atoms.

fur atoms possibly even tied in through the 'glyceryl radical. Also, itis probable that; the several fatty acid radicals present are alsolinked through sulfur atoms.- Compare comparable reactions involvingmore reactive sulfur dichloride, and particularly the formation ofcycIicbisuI- thioglycerol formation, or, more exactly, the formation ofsulfurized esters of thioglycerol, See Chemistry of Synthetic Resins,Ellis, 1935, volume 2, 1176-77. At any rate,in the course of thereaction polymers begin to be formed and a certain degree of elasticitybecomes apparent.-

Such reactions indicate the rationale for,

pound or composition by actionof, an, element 1 used,oftenroxygen;:,Thus, drying oils are often :Resinous and similarmaterials are sometimes classified 1 as thermoplastic, thermo-setting, Iand .elementl-convertible. The expression element convertible refersparticularly to plastic coatings" or drying oils in which'hardening, ap-

parently' is due to conversion p-into a new come referred to asbeing,foXy en-convertible. For practical purposesgthe' 'onlyiotherelement finding Wide: application: for thisg purpose iSuSlllflll. Hence,certain products, and, particularly certain oils, arehi'eferred ,toasfsulfur-convertible,

cmeaningthat thEYIIBWtkWith sulfur or sulfur -di-chloridelto:getpolymeric: materials, rubbery masses,.i'actice,or thilike'. 21$

The unsaturated high molal detergent-forming monocarboxylic acidsemployed by me in preparing my reagent are characterized by having acarbon atom chain, which I shall denote as R, containing at least 8carbon atoms and not more than 32 carbon atoms, and which must containat least one unsaturated bond, i. e., at least one ethylene linkage.Such acids are sometimes referred to as ethylenic.

The acyl radical may, of course, have present other non-functionalgroups, such as hydroxyl groups, acyl-oxy groups, etc. sary that thepresence of such groups does not detract from (a) the detergent-formingability of the acids, and (1)) their susceptibility to sulfurconversion. Suitability of substituted acids is indicated by very simpletests, For. instance,

-ducted on a small scale in the laboratory. If the substituted acid orester which has been previously determined to have detergent formingproperties also shows sulfur conversion susceptibility, 'it is, ofcourse, the obvious functional equivalent of the unsubstituted orunmodified acids or esters herein described and may be used with equalor even greater effectiveness.

Such high molal acids may be obtained from various sources, such asoils,-fats, and waxes; or one may use petroleum acids, rosin acids, andthe like. Petroleum acids include naturallyoccurring naphthenic acidsand also acids obtained by the oxidation of hydrocarbons and waxes.Rosin acids include abietic acid, pyroabietic acids, and the like.Saturated acids, such as saturated fatty acids, saturated naphthenicacids, saturated oxidized petroleum acids, vetc.,

' can frequently be converted into an unsaturatedacid by halogenization,followed by a reaction of the kind exemplified by theinternal Wurtzreaction.

My preference is to use unsaturated fatty acids, due to their low costand ready availability. One

need not use a single fatty acid, but may use the mixture obtained bysaponification of a natutonseed oil, fish oils, corn oil, soybean oil,linseed -oil, sesame oil, lard oil, oleo oil, perilla oil, and

many other naturally-occurring oils. Rapeseed oil, for example, containsappreciable proportions of tri-erucin, the tri-glyceride of erucic acid.

I have found it useful to prepare my reagent.

As has been previously pointed out, the high molal acids are used in theform of the polyhydric'alcohol ester having at least 2 such high molalacid radicals present. Since it is my preference to use thenaturally-occurring fatty acids, it obviously-follows that my preferenceis to use the naturally-occurring glycerides. However, if

' desired one can obtain thehigh molal acids fro-m any sourceand-esterifysuch acids with various polyhydric alcohols, such as the.glycols, in the conventional manner to produce suitable esters, whichmay or may not-have a free or unreacted alcoholiform hydroxyl grouppresent. The fatty acid di-glycerides typify "these esters which con- Itis only necesmanufacture of such esters is so well'known thattain a freeor unreacted alcoholiform hydroxyl group (in the residue of thepolyhydric alcohol, glycerol). The fatty acid tri-glycerides do notpossess this free alcoholiform hydroxyl. types of glyceride, forexample, are suitable for my purpose, provided the fatty acid presentsatisfies the above-expressed requirements. The

no description is required in the present instance. One may selectesters of the mixed type and such mixed esters may even contain acylradicals which either are not high molal in character or are notunsaturated, i. e., ethylenic in nature. For instance, diolein may bereacted with one mol of acetic acid or one mol of stearic acid to givean ester which would be satisfactory for the present purpose. As anexample'of a modified ester which may serve, reference is made totriacetylated triricinolein.

I have found that, in addition to naturallyoccurring' fatty acids,addition and substitution products of fatty acidswhich latter modifiedfatty acid beara simple genetic relationship to the parent fatty acidsfrom which they were derived-are also, useful for making my reagent,

so long as they are in part unsaturated, i. e., possess some doublebond, as shown by possession of an iodine number of appreciablemagnitude. i 7 Instead of employing natural poly esters of .reactivedetergent-forming carboxylic acidsin preparing my reagent, I may usesynthetic esters obtainedby esterifying oneor more reactivedetergent-formingcarboxylic acids with a polyhydric alcohol of the kindheretofore recited 'anddescribed in a conventional esterificationreaction, such as reacting the alcohol with the acidor acids in variousmolecular proportions in the presenc of, for example, dry hydrogenchloride.

The compound produced by the interaction of a a polyhydric alcohol ofthe above kindand "a reactive detergent-forming carboxylic acid of theabove kind will be termed a ipoly ester in-the from rally-occurring oilor fat. For instance, special I reference is made to the fatty acids,which occur naturally in olive oil, castor oil, peanut oil, cotpresentdescription. In all instances, it must contain-two or more radicals orresidues derived reactive detergentrforming carbo-xylic acids, which maybe the same or 'difierentacids; and it contains one or more radicals orresidues derived from polyhydric alcohols. Di-glycerides of unsaturatedfatty acids are examples o f-poly esters, just as are thenaturally-occurring triglycerides of unsaturated fatty acids Thereaction ofelemental sulfur with such .a

polyester is at first one of simple additionv of sulfur at the double,bond in the chain R of an.

acid residue in such poly ester to forms. sulfurized derivative whichdoes not differ greatly from the parent ester in properties. However,

, when the reaction is allowed to proceed at convthose polymericsulfurized bodies, obtained as above recited, which have a consistencyshort-cf rubber. Accordingly, I have termed them fsub- Both instances,it appears to have a disadvantage in that black specks appear in themixture in the course of manufacture (which, however, usually disappearon prolonged stirring under heat). I,

therefore, prefer to employ the procedure recited above as to preferredreagents. However, my invention contemplates a reagent produced eitherdescribed type or sulfurizing an aminated poly ester, of theabove-described type. I

The products so producedare ordinarily somewhat basic in character. vbasicity exists in the product, it may be used in its original form orit may be neutralized wholly or in part by reaction with a suitabl acid.I havefound, for example, that the acetate and the lactates prepared by.reacting such basic examples of my productwithacetic or lactic acidfrequently have notable merit. My invention is intended to include theuse of such salts,t her efore.

The complex aminated polymeric sub-rubbery sulfurized compound obtainedas recited above may be diluted with one ,or more solvents or diluentsto improve its vi scsity or other characteristics, as desired. Examplesof suitable diluents are isopropanol mineral spirits, benzol, etc.

In employing my reagent as a demulsifying agent, it is usually employedin the proportion of one part of reagent to from 2,000 to 20,000 partsof. petroleum emulsion, either in concentrated form or after diluting asdesired with a suitable vehicle or diluent or solvent. I desire to pointout that the superiority of my reagent-or demulsifying agent is based onits ability to treat or break certain emulsions more advantageously andat a lower "cost than is. possible with other available demulsifiers orconventional mixtures thereof.

In practising the process of demulsifying petroleum oil by means of mynew reagent, it is brought into contact with or is caused to act uponthe emulsion to be treated, in any-of the various ways or by any of thevarious apparatus now generally used to resolve or break petroleumemulsions with a chemical reagent, the abovev procedure being usedeither alone or.in combination with some other demulsifying procedure,such as the electrical dehydration process. e

While I have described in detailthe preferred embodiment of myinvention, it is understood that the materials employed, theproportionsof ingredients, the arrangements of steps, and the details ofprocedure may be variously modified without departing from the spirit ofthe subjoined claims.

I claim: I 1. A composition of matter, ,consisting of analkanolamine-reacted sub-rubbery polymeric sulfur-converted polyhydricalcohol ester; said ester prior to sulfur-conversion containing at least2 unsaturated high molaldetergent-forming monocarboxylic acid radicalshaving at least 8 carbon atoms and not more than 32 carbon atoms each;the reaction involving the alkanolamirie being conducted with almostimmediate completeness at a temperature of 150 C. to below 190C andratios of reactants being as follows: For each 100 parts by Weight ofthe high molal detergent-forming monocarboxy ester, there is employedlOto 17 parts by weight of sulfur and to 20 parts by weight ofthealkanolamine.

. by aminating. a sulfurized poly ester of the above- To the extent thatv alkanolamine.

and said ester prior to sulfur-conversion being? free from any unreactedhydroxyl radical as part of the alcoholic residue; the reactioninvolving the alkanolamine being conducted with almost immediatecompleteness at a temperature of 150 C. to below 190? C., and ratios ofreactants being as follows: For each parts by weight of the high molaldetergent-forming monocarboxy ester, there is employed 10 to 17 parts byweight of sulfur and 10 to 20 parts by weight of the alkanolamine.

3. A composition of matter, consisting of an alkanolamine-reactedsub-rubbery polymeric sulfur-converted polyhydric alcohol ester; saidester prior tosulfur-conversion containing at least 2 unsaturated fattyacid radicals having at least 8 carbon atoms and not more than 32 carbonatoms each; and said ester prior to sulfur-conversion being free fromany unreacted hydroxyl radical as part of the alcoholic residue; thereaction involving the alkanolarnine being conducted with almostimmediate completeness at a temperature of C. to below C., and ratios ofreactants being as follows For each 100 parts by weight of the highmolal detergent-forming monocarboxy ester, there is employed 10 to 1'7parts by weight of sulfur and 10 to 20 parts by weight of the 4. Acomposition of matter, consisting of an alkanolamine-reacted sub-rubberypolymeric sulfur-converted polyhydric alcohol ester; said ester prior tosulfur-conversion containing at least 2 monoethylenic fatty acidradicals having at least 8 carbon atoms and not more than 32 carbonatoms each; and said ester prior to sulfur-conversion being free fromany unreacted hydroxyl radical as part of the alcoholic residue; thereaction involving the alkanolamine being conducted with almostimmediate completeness at a temperature of 150? C. to below 190 C., andratios of reactants being as follows: For each. 100 parts by Weight ofthe high molal detergent-forming monocarboxy ester, there is employed 10to 17 parts by weight of sulfur and 10 to 20 parts by weight of thealkanolamine.

5. A composition of matter, consisting of an alkanolamine-reactedsub-rubbery polymeric sulfur-converted polyhydric alcohol ester; saidester prior tosulfur-conversion containing at least 2 radicals derivedfrom monoethylenic fatty acids having 18 carbon atoms each; and saidester prior to-sulfur-conversion being free from any unreacted hydroxylradical as part of the alcoholic residue; the reaction involving thealkanolamine being conducted with almost immediate completenessat' atemperature of 150 C. to below 190 0.; and ratios of reactants being asfollows: For each 100 parts by weight of the high molaldetergent-forming monocarboxy ester, thereis employed 10 to 17 parts. byweight of sulfur and 10 to 20 parts by weight of the alkanolamine.

6. A'composition of matter, consisting of an alkanolamine-reactedsub-rubbery polymeric sulfur-converted glycerol ester, said ester priorto sulfur-conversion containing 3 .monoethylenic fatty acid radicalshaving 18 carbon atoms each;

and, said ester prior to sulfur-conversion being' free; from anyunreacted hydroxyl radical as part alkanolamine being conducted withalmost immediate completeness at a temperaturefof 150 C. to below 190C., and ratios of reactants being as follows: For each 100 parts byweight of the high molal detergent-forming monocarboxy ester,

there is employed Etc 17 parts by weight of sulfur and to 20 parts. bynweight of the alkanolamine.

7.A composition of matter, consisting of an alkanolamine-reactedsub-rubbery polymeric sul fur-converted triricinolein; the reactioninvolving the alkandlamine being conducted Wi'bhfil! most immediatecompleteness at a temperature of150 C. to below 190 C., and ratios ofreactants being as follows: For each 100 parts by weight of the highmolal detergent-forming mono-carboxy ester, there is employed 10 to 17parts by weight of sulfur and 10 to 20 parts by Weight of thealkanolamine.

8. A composition of matter, consisting of atriethanolamine reacted subrubbery polymeric sulfur-converted polyhydric alcohol ester; 'said esterprior to sulfur-conversion containing at 2,363,034 of the alcoholicresidue the reaction involving the i least 2 unsaturated high molaldetergent-forming monocarboxylic acid radicals having at least 8ethanolamine-reacted sulfur-converted tri-ricinolein; the reaction in-[carbon atoms and not more than 32 carbon atoms each; the reactioninvolving the alkanolamine being conducted with almost immediatecompleteness at a temperature of 150 C. to below 190 0., and ratios, ofreactants being as follows:

For each parts by weight of the high molal detergent-forming monocarboxyester, there; is employed 10 to 17 parts by weight of sulfur and 10 to20 parts by weight of the alkanolamine.

9. A composition of matter, consisting of a trisub-rubbery polymericvolving the aikanolamine being conducted with almost immediatecompleteness at a temperature of C. to below 0., and ratios of reactantsbeing as follows: For each 100 parts by weight of the high molaldetergent-forming monocarboxy ester, there is employed 10 to 17 parts byweight of sulfur and 10 to 20 weight of the alkanolamine.

ALLEN.

parts by

